Use of nonionic surface active agent in preparation of anionic resin in bead from



Patented Sept. 9, 1952 UNITED STATES PATENT OFFICETQ' USE OF NONIONIC SURFACE ACTIVE AGENT IN PREPARATION OF ANIONIO RESIN IN- BEAD FORM Lennart A. Lundberg, Stamford, Conn., assignor to American Cyanamid Company, New York, 7 N. Y., a corporation of Maine No Drawing. 1

Application February 17, 1949, Serial No. 77,069

5 Claims. (01. 260-2) 7 immiscible media. Resins of the thermosetting condensation type such as urea-formaldehyde, melamineeformaldehyde and the like, and particularly resins of the thermosetting condensation type in a cured'state such as the ion exchange resins, both anionic and cationic, have however not previously been produced in the form of spheroidal particles or beads of uniform size.

It is an object of the present invention to produce an anion exchange resin active for the removal of anions from, or the exchange of anions in, fluid media in a form which can be used directly', without grinding or screening, in ion exchange processes.

.It is another object of the presentinvention to produce an anion exchange-resin in the form of spheroidal particles. i i r A further object of the present invention is to provide a method for preparing a condensation type, thermosetting, synthetic resin in the form of spheroidal heads.

I Stillanother object of the present invention is to convert a partially condensed, water-soluble resin to a cured, water-insoluble anion active resin in head form.

It is still a further object of the present invention to prepare in bead form an anionexchangeresin which is a condensation product of epichlorohydrin or glycerol dichlorohydrin with a polyalkylene polyamine.

Another object of the present invention is the preparation, in head form, of an anion exchange resin which is a condensation product of guanidine, melamine, and formaldehyde.

The above and other objects are attained by dispersing an aqueous syrup of a resinous partial condensation product of ingredients which,

when fully condensed, produce an insoluble anion:

The invention will be described in greaterde 2 tail in conjunction with the following specific examples in which proportions are given inparts' by weight. It should be understood that the examples are merely illustrativeand it is not intended that the scope of theinvention be limited to the details therein set forth. i

EXAIVLPLE 1 (1) 175 parts of resin A? syrup (2) 489 parts of o-dichlorobenzene.

(3) 4.9 parts (1.0% of the weight of 0-dl0h1010r benzene) of the reaction product. ofethanol stearamide and 8 mols of ethylene oxide, said reaction product having the formula: r

CH3 (CH2) 16CONHCH2CH2 (002m) aoii (2) and (3) are charged into a suitablevessel equipped with an' anchor type 'stirrenawater trap and means for indication of temperature: The mix is hcatedto 80C. and the stirrer? ad justed to 150 R. P. Mawhereupon (1) isad'ded filtered off and cured in an oven at 0:

rapidly. The resulting dispersion is refluxed for one hour at 95 C. and 72 parts of water are removed azeotropically. Refluxing is resumed at C. for 3.5 hours.

Translucent beads are obtained, 41.9%" oi which are 20-40 mesh. A l

EXAMPLE 2 EXAMPLE 3 (1) parts of resin C syrup (2) 635 parts of ethylene dichloride f (3) 1.9 parts 0.3% of the weight of (2) of the addition product of ethanol stearamide andii mols of ethylene oxide having the. formula:;

CH3 (CH2) mCONHCHzCI-Iz (OC2H4) 80H (2) and (3) are charged into a suitable vessel equipped with an anchor type stirrer, a water} trap, and means for indicating temperature. The mix is heated to reflux, the stirrer is ad justed to 200-210 R. P. M. and (1) is added rapidly. The resulting dispersion is reiiuxedfor one hour after which the bead product formed is EXAMPLE 4 The procedure of Example 3 is followed, and

cured resin beads suitable for use in anion. exchange processes are obtained.

Preparation of resin A syrup (1) 189 parts of tetraethylene pentamine '(l;0

mol)

(2) 277 parts of epichlorohydrin (31011111018).

(2) 466 parts of water (2) is added slowly to (l) and (3) with-cooling to maintain the temperature at 45-55 0. About a half hour iszrequired for the addition. The sympL-iathenmaintained.at 50 for 0.75-l.5.hours.

Preparation of resin B syrup The-same procedure i's followed asiorthe'preparation of resin -A- syrup except that only 366 parts of water areused.v

Preparation of resin C syrup (51 is placed inasuitablevessel equipped'with means of .agitating and means for, indicating temperatureand (2*) and. ('3')".are addedithereto; The resultingislurry is heated with steam until tsolu- MOITOOCUI'S, at which'point 1(4) is addedand-lthe temperature :drops 'to' about 65C; where it is maintained for 10 minutes- The clearywater white'syrup is. cooled immediately to125 C. and (5) and (6) are slowly added while the temperaturefris' maintained at 27 -33? C. Thesyrup has a viscosity of 3.0 poises.

Anion active, synthetic resins to which the process of the present-invention is applicable include those described :in U. 5. Patents Nos. 2,285,750, 2,395,825, 2,341,907, 2,402,384 and 2,251,234 as Well as those described and-.claimed in mycopendingapplication with-James R. Dudley, U. S.:application Serial No. 616,644filed September 15, 1945. Other anion resins to which the process. may be applied include condensation products of acetaldehyde, formaldehyde and polyalkylene pol-yamines -.(Serial N 0-. 643,836 ifiled January 26, 1946); of aminotriazine, aldehyde, and guanido compounds (Serial No. 607,277 filed July 26, 1945); of aminotriazine, aldehyde, strongly basic nQn-aromaticamines (Serial No. 649,127 filed February .20, 1946); of biguanide, carbonylcompounds and aldehydes (Serial No.

703,481 :filed October 16', 1946'); of crotonaldehyde, formaldehyde, and polyalkylene polyamine (Serial 'No. 643,8381filed' January 26, 19,461; of polyepoxy'compounds and alkylene polyamines (Serial No. 655,005 filed: March; 16', 19.46); of glycerol dichlorohydrin and: alkylener polyamines (Serial .No. 624,606 filed October .25, 1945), of iurfural guanido' compounds and. carbonyl .compounds (Serial No. 703,489 filed. October 16, 1946); and of furyl aliphatic amines and aldehydes (Serial.No.642-,416 filed January 19, 1946).

In general, nay-process maybe applied ,toany,

4 anion active resin of the condensation type which has a sufiiciently rapid rate of gelation for bead formation. When the gelation rate is too slow, the resin globules agglomerate before they become hardened by gel formation. 1

Non-ionic surface active agents which are ethylene oxide addition products generally are useful in the present process. Examples of such products, which areethylene oxide addition products of ;acids, amines, amides, alcohols, etc., containing a higher alkyl group (8-18 carbons), includeinadditionto those of the specific examples, polyethylene .glycol substituted maleic acid esters, the ethylene oxide condensation products of manitanandsor-bitanmonoesters of higher fatty acidssuch as palmitic, stearic and oleic acids,

the addition products of octadecylamine with ethyleneoxide, of stearoguanamine and ethylene oxide, and the like.

The optimum amount of ethylene oxide addition product used :will, vary, depending upon the rate and type of agitation, the non-solvent medium and particularly its density, the resin dispersant and particularly its viscosity, the desired bead size, etc. The-minimum quantity of dispersing agent for anyparticular system is .that amount which will keepthe resin dispersed .in the non-solvent medium; the-maximum quantity issdependent upon the desired beadsizesince, in general, the larger the quantity of dispersing agent the smaller the bead; In general, I use from .-about 0.005% to about 3%, based on the weight of non-solvent medium, of surfaceactive agent. 7

Organic .non-solventrmedia which may be used inv the practice ofthe iprocessof :the presentin- Ventionmust be liquid-at room-temperature, insoluble. in water, stable toward heat (up .to about 70 Oat-least) not-readilyhydrolyzalble and inert, i. e;, non-reactive with. the-initial resinforming materials 'or their partialeorv final condensation products. In addition they should preferably boil above about 70 C. and'ahave specific gravities substantially equivalent2to'those of 'the resin syrup, generally from about 11.1 'to 1.5-. 'I-The non-solvent media mayeach consist of a single compound, or they may be. mixtures. of: two or more compounds, as inExample 2 if the properties of the combination'fit. the :necessary qualification.

Following are some nonesolventgmedia which may advantageouslyibe usedinxthe-process of the presentinvention:

Boiling Specific Point 0 Gravity propylidene dichloride 87 1. 143 tnmethylenedichloride. 123-5 .1. 201 propylenechloride; 96.8 1.159. Ld-propylenedichloride. 109 '1. 204 tr1chlorethylene. 87.2 1.466 l',1,2-trichlorethane 113:5 l. 441 1,1.l=trich1orethane N 74. 1' l; 325 o-dichlorbenzene. 179 l. 305 ethylene dichloride; 83.7 1. 256' l,2,4-t riohlorbenzene 213 1. 446 3,3-d1chlorodi-n-propy] ether. 215 1. sym dichlorethyl ether. 178: 5 1. 222 2- 'dICh1OIBthEnO1?1 146. l. mtrobenzene 211 l; 205 o-mtroethylbenzen 227 l; 126 o n trcphenetol.- 275 1.190 oenitrotoluene .1 22,3. 1. 103 lgz dimeth yld-nitrobenzena 240 1. 147 p-iluoroohlorbenzene 4- 1 130 1. 226 fluoronaphthalene 212 1.133 L-bromohexaue 156 1. 173 l-giomnnfann .188 1. 099 1- ompropane'. 1 71 1. 353 dipheuyl ether 235 1. 205

ards, Standard Screen Series, 1919).

I Non-solvent 1 media or higher: thanfthe .preferred' specific (gravity 'may be diluted with less dense liquids such as toluene'and/ or xylene until thedensity of the combination is substantially equivalent to that of the resin syrup and then used satisfactorily in the present process. A few of these media of higher specific gravity are;

1 Boilin Point C.

Specific Gravity sym. tetrachlorethane 146,3 sym.tetrabromethane. 151' (54 mm.) 1,1,2-tribromethana; .I Y 188 Boiling Specific Point C. Gravity toluene 110. 8 0. 866 o-xylene. 144 0. S81 m-xylene 139. 3 ,0. 867 p-xylene .r 138. 5 0. 861 1,2,3-trimethylbenzene. 176. 1 0. 894 1,2,4-trimethylbenzene 169. 8 0.876 1,3,5-trimethylbenzene. 164. 8 0. 865 ethyl benzene 136. 2 0. 867 isopropylbenzene 152. 5 0. 862 p-cymene 176-7 .0. 857

In the event that an extremely inert non-solvent medium is required, suitable liquids include xylene hexafiuoride, xylene hexachloride, toluene trifluoride, those fluorcarbons and fiuorochlorocarbons having the necessary boiling point and specific gravity, mixtures of these inert media with each other and with other media mentioned above as suitable.

The mechanical agitation taking place during the process of the present invention is very important. The degree and type of agitation must be sufiicient to keep the dispersion from coagulating but it has a variable upper limit depending upon the size of beads desired and the practicality of producing them. With an anchor type stirrer, as used in the examples, a speed of from about 100-200 R. P. M. is generally preferred for the production of resin beads within a range suitable for use in ion exchange processes, i. e., from about 8-60 mesh, wet-screened, on a stand ard U. S. Sieve Series (U. S. Bureau of Stand- However, the speed can go as high as about 600 R. P. M. in which case a much smaller head is formed from a comparable resin syrup. Furthermore, in many cases variable speed agitation is desirable, gel formation being eifected at relatively low speed followed by increased speed to prevent agglomeration of the dispersed particles during the cure. Impeller, impeller-baffle, turbine and other type agitating means may be substituted for the anchor type of the examples.

When extremely small or micro beads are desired, as for medicinal ion exchange application, a high agitation rate with relatively large I of surface active age'ntare" critical-E6 tion to take place. 1 i

The success of my process appearst depend at least in parton thee stablishment; under any given set of conditions, of an interfacial' tension in theresin-medium system which is within a definite range'conducive to the formation of spheroidal particles. My process is specific to the particular type surface active agent claimed, however, sincenot allsurface activeagents which 0 produce an interfacial tension within 'the determined range will necessarily work. I have found that the cationic hydroxyalkyl amine-salts and the quaternary ammonium salts disclosed densation products containing omega sulfonic acid groups in spheroidal form according to the present process.

It may be desirable, according to the process of the present invention, to remove at least a portion of the water from the dispersed resin syrup in order to increase the reflux temperature of the system, particularly if the resin is to be cured in the non-solvent liquid or if it has a relatively slow rate of gelation.

Once gelation has occurred the resin beads are cured by heating in the presence or absence of a non-solvent liquid at from about 50-130 C., the preferred curing temperature within the range depending upon the particular resin. For instance I cure beads of epichlorohydrin-polyalkylenepolyamine resin at about -130 C., preferably at about -125 C., beads of guanidine-melamine-formaldehyde resin at about 50-110 C. and preferably in two stages, the first around 50 C. and the second around 100 C.

The process of the present invention may be applied to the preparation of dyes, pigments, catalysts and ionic or non-ionic resinous ma terials in the form of spheroidal or micro-spheroidal particles which because of their spheroidal nature, possess special advantages over the corresponding granular products.

Similar processes applied to other type resins and/or other type surface active agents are described and claimed in the copending application of Arthur S. Nyquist, Serial No. 77,071, filed February 17, 1949, entitled Preparation of Non- Nuclearly Sulfonated Phenol-Formaldehyde Resin in Bead Form and in my copending applica= tions identified below:

capable of being cured to a water-insoluble anion active product in an inert, organic non-solvent liquid which has a boiling point of at 1east70 C. and the density of which is substantially equivalent to that of said aqueous resin syrup, with 7 ica1-agitatio1 1 ;i1 1 the DQ553398; 9f 41- mil a ent wh chis an et lene 5 i6 aqdl @111" igrbdu maintain ng the dis= plqrsipn at a e e a d mperat r nti t resin gels, and finally curing the gelledg esjn 9b ta d-byhea in ufiiciemag a on-bang pr A DIQQQS'S acg rsi ng wi h slain; 1 .in

whic

11 water 1.5;.aze mpically o exl 30 11.2 .19

LENNART A- L'UNDBEBG- BEFEEENCES ,QII'IED The'- following references are of "record in--the file of this pat nt;

UNITED STATES PATENTS Number Name. Date V FOREIGN PATENTS Number Country Date 

1. A PROCESS WHICH COMPRISES DISPERSING AN AQUEOUS SYRUP OF A PARTIALLY CONDENSED RESIN CAPABLE OF BEING CURED TO A WATER-INSOLUBLE ANION ACTIVE PRODUCT IN AN INERT, ORGANIC NON-SOLVENT LIQUID WHICH HAS A BOILING POINT OF AT LEAST 70* C. AND THE DENSITY OF WHICH IS SUBSTANTIALLY EQUIVALENT TO THAT OF SAID AQUEOUS RESIN SYRUP, WITH MECHANICAL AGITATION IN THE PRESENCE OF A NONIONIC SURFACE ACTIVE AGENT WHICH IS AN ETHYLENE OXIDE ADDITION PRODUCT, MAINTAINING THE DISPERSION AT AN ELEVATED TEMPERATURE UNTIL THE RESIN GELS, AND FINALLY CURING THE GELLED RESIN OBTAINED BY HEATING, SUFFICIENT AGITATION BEING PROVIDED THROUGHOUT THE HEATING TO PREVENT COAGULATION OF THE DISPERSION. 